Evidence for Enhanced Tracer Diffusion in Densely Packed Interfacial Assemblies of Hairy Nanoparticles

Nearly monodisperse nanoparticle (NP) spheres attached to a nonvolatile ionic liquid surface were tracked by in situ scanning electron microscopy to obtain the tracer diffusion coefficient D as a function of the areal fraction ϕ. The in situ technique resolved both tracer (gold) and background (silica) particles for ∼1-2 min, highlighting their mechanisms of diffusion, which were strongly dependent on ϕ. Structure and dynamics at low and moderate ϕ paralleled those reported for larger colloidal spheres, showing an increase in order and a decrease in D by over 4 orders of magnitude. However, ligand interactions were more important near jamming, leading to different caging and jamming dynamics for smaller NPs. The normalized D at ultrahigh ϕ depended on particle diameter and ligand molecular weight. Increasing the PEG molecular weight by a factor of 4 increased D by 2 orders of magnitude at ultrahigh ϕ, indicating stronger ligand lubrication for smaller particles.